CN117512344A - Method for separating manganese and magnesium components in gas slag - Google Patents
Method for separating manganese and magnesium components in gas slag Download PDFInfo
- Publication number
- CN117512344A CN117512344A CN202311826077.XA CN202311826077A CN117512344A CN 117512344 A CN117512344 A CN 117512344A CN 202311826077 A CN202311826077 A CN 202311826077A CN 117512344 A CN117512344 A CN 117512344A
- Authority
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- Prior art keywords
- slag
- solution
- magnesium
- manganese
- hydroxide
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- Granted
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- 239000002893 slag Substances 0.000 title claims abstract description 147
- 239000011777 magnesium Substances 0.000 title claims abstract description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011572 manganese Substances 0.000 title claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000000967 suction filtration Methods 0.000 claims abstract description 24
- 239000003034 coal gas Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000003245 coal Substances 0.000 claims abstract description 14
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 238000002309 gasification Methods 0.000 claims description 28
- 239000007790 solid phase Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000011575 calcium Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of magnesium extraction, in particular to a method for separating manganese and magnesium components from coal gas slag; uniformly mixing coarse coal gas slag and fine coal slag, crushing and grinding, uniformly mixing the crushed coal gas slag with sodium carbonate, and activating and roasting in medium-low temperature continuous heating equipment; dissolving the activated gasified slag in hydrochloric acid, and continuously stirring to accelerate the reaction; removing insoluble impurities by suction filtration to obtain valuable metal enrichment solution; adjusting the pH value to remove metal impurities such as iron and aluminum; after suction filtration, introducing carbon dioxide into the liquid phase, and suction filtering again to remove impurities of calcium; adjusting the pH value of the liquid phase to enable manganese element to be precipitated in the form of manganese hydroxide; filtering again, and adjusting the pH value of the liquid phase to enable magnesium element to be precipitated in the form of magnesium hydroxide; washing and drying manganese hydroxide and magnesium hydroxide for multiple times to obtain a high-purity manganese magnesium product; the invention extracts the manganese and magnesium components in the gas slag through a set of process flow.
Description
Technical Field
The invention relates to the technical field of magnesium extraction, in particular to a method for separating manganese and magnesium components from coal gas slag.
Background
The coal gasification slag is a solid residue formed by inorganic mineral matters and residual carbonaceous particles in the coal gasification reaction process. In recent years, the coal chemical industry rapidly develops, the annual discharge amount of gasification slag is increased, and the large-scale treatment and resource utilization are urgent. At present, the large-scale treatment and utilization of gasified slag is mainly focused on the aspects of construction and building materials, ecological management and the like; however, the gasification slag has high carbon content, high impurity content and the like, and thus the gasification slag cannot be treated in large scale.
The coal gasification residue comprises coarse residue and fine residue, the residue component is related to the ash content, composition, gasification process and the like of the gasification raw material coal, and mainly comprises SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 Composition, etc.; the gas slag also contains MgO, mnO, tiO 2 And the like, the characteristics are important material basis of the coal gas slag recycling technology.
The problems with the prior art are therefore: how to separate the manganese and magnesium components of the coal gasification residue.
Disclosure of Invention
The invention provides a separation method of manganese and magnesium components in coal gas slag.
The technical scheme adopted by the invention is as follows: a method for separating manganese and magnesium components in coal gas slag comprises the following steps:
s1: mixing coarse slag and fine slag of the gas-converted slag, and crushing and grinding;
s2: uniformly mixing the crushed coal gas slag of the S1 with active metal carbonate, and heating and activating by using medium-low temperature continuous heating equipment;
s3: dissolving the gasified slag in water after activation, and continuously stirring and dispersing to form a solid-liquid mixture;
s4: adding hydrochloric acid into the solid-liquid mixture obtained in the step S3 for dissolution, and stirring in a hot water bath; suction filtration is carried out to obtain a first solution and a first solid phase;
s5: adding an alkaline solution, regulating the pH value of the first solution to 7-9, and then carrying out suction filtration to obtain a second solution and a second solid phase;
s6: introducing CO into the second solution 2 Then suction filtration is carried out to obtain a third solution and a third solid phase;
s7: adding an alkaline solution, regulating the pH value of the third solution to 9-12, and then carrying out suction filtration to obtain a fourth solution and a fourth solid phase; the fourth solid phase contains manganese hydroxide, and the main component in the fourth solution is magnesium ions;
s8: adding an alkaline solution to adjust the pH value of the fourth solution to 13-14, and generating magnesium hydroxide sediment;
s9: washing and drying manganese hydroxide and magnesium hydroxide.
In the step S1, the mixing ratio of the coarse gas-chemical slag and the fine gas-chemical slag is 5:1-1.5.
Further, the carbonate of the active metal in step S2 may be any of sodium carbonate and potassium carbonate.
Further, in the step S2, the mixing ratio of the gasified slag and the sodium carbonate is 15-30:1.
In step S2, the roasting temperature of the medium-low temperature continuous heating equipment is 550-750 ℃, the heating rate is 10-20 ℃/min, and the roasting time is 20-60min.
Further, in step S4, the mass fraction of hydrochloric acid was 31%, and the temperature of the hot water bath was 80 ℃.
Further, the alkaline solution used in steps S5, S7, S8 is a sodium hydroxide or potassium hydroxide solution.
Further, in step S5, the pH of the first solution is adjusted to 8.
Further, in step S7, the pH of the second solution is adjusted to 12.
Further, the pH of the third solution is adjusted to 14 in step S8.
The beneficial effects achieved by the invention are as follows:
firstly, uniformly mixing coarse slag and fine slag of coal gas slag, and crushing and grinding; the microstructure and the grain diameter of the ore powder are changed mainly by a mechanical method, then the crushed gas slag is uniformly mixed with sodium carbonate, activated and roasted in medium-low temperature continuous heating equipment, and a large amount of reaction heat can be provided by utilizing the residual carbon of the fine slag, so that the chemical activity of the gas slag is improved; adding hydrochloric acid into the activated gasification slag for dissolution, and carrying out chemical reaction: mnO+2HCl→MnCl 2 +H 2 O and MgO+2HCl→MgCl 2 +H 2 O, continuously stirring to accelerate the reaction, so that the reaction is full; removing insoluble impurities by suction filtration to obtain valuable metal enrichment solution; adjusting pH value to generate chemical reaction Fe 3+ +Na0H→Fe(0H) 3 ↓+Na + ，Al 3+ +Na0H→Al(0H) 3 ↓+Na + Removing metal impurities such as iron and aluminum by means of a waiting reaction; after suction filtration, carbon dioxide is introduced into the liquid phase to generate chemical reaction CO 2 +H 2 O→H 2 CO 3 ，Ca 2+ +CO 3 2- →CaCO 3 Filtering again to remove impurities of calcium; adjusting the pH value of the liquid phase to generate chemical reaction Mn 2+ +2OH - →Mn(OH) 2 ∈2, so that manganese element is precipitated in the form of manganese hydroxide; filtering again, adjusting the pH value of the liquid phase, and generating chemical reaction Mg 2+ +2OH - →Mg(OH) 2 ∈so that magnesium element is precipitated in the form of magnesium hydroxide; washing and drying manganese hydroxide and magnesium hydroxide for multiple times to obtain a high-purity manganese magnesium product; the process has low reaction energy consumption andthe reaction is rapid and easy to control, and the obtained product has higher purity and higher value; the process has no emission of harmful substances in the production process, part of raw materials can be recycled, and the comprehensive utilization value of the gas slag can be effectively improved;
the invention adopts a main separation mode for grading purification, so that not only the residual carbon of the fine slag can be effectively utilized, but also the defect of conventional high-temperature activation is overcome. The process has the advantages of high product grade, repeated recycling of byproducts, low energy consumption and rapid reaction; meanwhile, the process has the advantages of simple operation, easy control of reaction, industrialized continuous production, environmental friendliness, high economic benefit and the like.
Drawings
FIG. 1 is a graph of the ratios of the components of the coarse and fine gas-converted slag of the present invention.
Fig. 2 is a process flow diagram of the present invention.
Fig. 3 is an SEM image of the fine slag of the present invention.
FIG. 4 is a schematic view of the structure of the activated gasification slag of the present invention.
FIG. 5 is an SEM-EDS of magnesium element of the present invention.
FIG. 6 is an SEM-EDS of manganese element of the present invention.
Fig. 7 is a mass ratio and atomic ratio diagram of manganese element and oxygen element in the present invention.
FIG. 8 is a schematic diagram of the coarse slag roasting of the gas-converted slag of the present invention.
FIG. 9 is a schematic diagram of the fine slag roasting of the gas-converted slag of the present invention.
FIG. 10 is a schematic diagram of the mixed roasting of coarse and fine gas-converted slag of the present invention.
Detailed Description
In order to facilitate understanding of the invention by those skilled in the art, a specific embodiment of the invention is described below with reference to the accompanying drawings.
First, an application scenario of the present application is described: generally, the production amount of the gas slag coarse slag accounts for about 80 percent of the total emission amount of the gasification slag, the residual carbon content is lower and is generally 5 to 30 percent, and the grain size of the gas slag coarse slag is 16 to 4 meshes; the coal gas slag powder accounts for about 20% of the total discharge amount of the gasified slag, the gasification residence time of the coal gas slag powder in the gasification furnace is short, the mass fraction of carbon residue is high, the mass fraction of the carbon residue is about 30% -50%, and the grain size of the coal gas slag powder is smaller than 200 meshes; the sources and the states of gasified slag generated by different coal gasification processes are different; the ratios of the components (after decarbonizing) of the coarse coal gasification slag and the fine coal gasification slag adopted in the test are shown in figure 1.
As shown in fig. 2, the invention provides a method for separating manganese and magnesium components in gas slag, which comprises the following steps:
s1: uniformly mixing coarse slag and fine slag of the gas slag, and crushing and grinding;
specifically, the coarse coal gas slag is crushed by a crusher and then ground by a mill (250-4000 microns), and the particle size of the ground coarse coal gas slag is 1000-70 meshes, preferably 300 meshes; the particle size of the coarse slag is reduced by adopting a physical method, and the particle size of the coarse slag is still larger than that of the fine slag; the mixing ratio of the coarse coal gas slag to the fine coal gas slag is 5:1-1.5; preferably 5:1.
S2: uniformly mixing the crushed gas slag with active metal carbonate, and heating and activating by using medium-low temperature continuous heating equipment; forming activated gasification slag;
specifically, the carbonate of the active metal may be one of sodium carbonate and potassium carbonate, preferably sodium carbonate; the mixing ratio of the gasified slag and the sodium carbonate is 15-30:1, preferably 20:1; mixing the coarse coal gas slag, the fine coal gas slag and sodium carbonate through a stirrer; the medium-low temperature continuous heating equipment can be one of a continuous tunnel heating furnace, a rotary kiln and a trolley furnace, the roasting temperature is 550-750 ℃, the heating rate is 10-20 ℃/min, and the roasting time is 20-60min;
firstly, the production amount of the coarse coal gasification slag accounts for about 80% of the total emission amount of the gasification slag, the residual carbon content is lower, the fine coal gasification slag accounts for about 20% of the total emission amount of the gasification slag, and the residual carbon content is higher; the components contained in the coarse slag and the fine slag are the same, and the coarse slag and the fine slag of the gas slag can be extracted simultaneously by a set of processes;
as shown in the SEM image of the fine slag, the fine slag is flocculent in microcosmic, the crushed coarse slag of the gas slag is mixed with the fine slag, so that the coarse slag and the fine slag can be mixed more uniformly, the fine slag is adhered to the coarse slag with larger particles, and then sodium carbonate is added for stirring;
compared with the method which takes coarse slag as raw material independently, the method has the advantages that the roasting temperature can be greatly reduced and the energy consumption can be reduced by doping fine slag; after the coarse slag and the fine slag of the coal gas are mixed, carbon in the fine slag exists in each part in flocculent form, under the condition of uniform mixing, each part burns simultaneously to release heat, the carbon content in the fine slag accounts for about 30-50%, the carbon in the part burns during roasting, the heat value of 32825.56KJ heat of 1kg of carbon is completely burnt, the heat in the part directly acts on the surface and the inner reaction area of the gasified slag, the reaction efficiency is increased, the roasting time is shortened, the temperature provided by the outside during roasting is greatly reduced, namely, the carbon is fully burnt at a lower temperature; the roasting temperature of the raw materials of the coarse slag is required to reach 750-850 ℃ independently, and after the fine slag is doped, the roasting temperature is reduced to 550-750 ℃, so that the energy consumption is reduced.
Wherein sodium carbonate is used as an activating agent, and the physical and chemical properties of gasified slag can be changed by utilizing medium-low temperature continuous heating equipment for heating activation treatment; before activation, the surface of the coarse slag is compact, and the coarse slag presents a glass phase structure, so that the structure prevents various elements from being dissolved, and the difficulty in separating the elements is increased; FIG. 4 is a schematic diagram of the structure of the gasified slag after activation, wherein the chemical stability of minerals can be reduced and the activity of the minerals can be increased through the activation treatment; the glass phase structure on the surface of the coarse slag is destroyed, a low-density porous structure is formed, the specific surface area is increased, the subsequent dissolution of the acid is facilitated, and the subsequent extraction of manganese and magnesium elements is easier.
S3: dissolving gasified slag tailings after the activation in the step S2 in water, and continuously stirring and dispersing;
specifically, stirring until no precipitate is dissolved, and stopping stirring to obtain a solid-liquid mixture; the main components of the sediment are calcium (CaO) and aluminum (AlO) 3 ) Iron (Fe) 2 O 3 ) Valuable elements such as magnesium (MgO); the liquid mainly comprises sodium silicate.
S4: adding hydrochloric acid into the solid-liquid mixture obtained in the step S3 for dissolution, and stirring in a hot water bath; then carrying out suction filtration to obtain a first solution and a first solid phase;
specifically, adding hydrochloric acid with the mass fraction of 31% until the precipitate is no longer dissolved, and stirring for 10 minutes; the temperature of the hot water bath is 80-90 ℃, the heating temperature of the water bath is adjustable, the heating is stable, and the dissolution speed can be accelerated; the suction filtration can be carried out through a buchner funnel, a suction filtration bottle, a circulating vacuum pump and the like for solid-liquid separation;
the reaction occurring in step S4 is as follows: mnO+2HCl→MnCl 2 +H 2 O MgO+2HCl→MgCl 2 +H 2 O
The method comprises the steps of carrying out a first treatment on the surface of the The manganese element and the magnesium element which are mainly separated are completely dissolved in the solution in the form of manganese ions and magnesium ions; al (Al) 2 O 3 、CaO、Fe 2 O 3 Respectively aluminum chloride, calcium chloride, ferric chloride and the like in the first solution; detecting that the pH value of the first solution is less than 1, wherein the first solution contains valuable metal ion solutions such as manganese ions, magnesium ions, aluminum ions, iron ions, calcium ions and the like; the first solid phase is SiO 2 。
Dissolving the gasified slag after the activation in the step S3 in water to prepare a solid-liquid mixture, and then reacting with hydrochloric acid, wherein the reason why the gasified slag after the activation in the step S2 does not directly react with the hydrochloric acid is as follows: directly adding hydrochloric acid into the activated gasification slag can release a large amount of hydrogen sulfide gas, firstly adding the hydrochloric acid into water, then adding the hydrochloric acid can reduce the hydrogen sulfide gas, and the hydrogen sulfide is an inorganic compound in a gas state; colorless, low concentration, odorous egg smell and extremely toxic.
S5: adding alkaline solution to adjust the pH value of the first solution to 7-9, and then carrying out suction filtration to obtain a second solution and a second solid phase; further, the alkaline solution used in step S5 is sodium hydroxide or potassium hydroxide solution, preferably sodium hydroxide solution, preferably pH 8; at this time, iron and aluminum are completely precipitated;
the reaction occurring in step S5 is as follows: fe (Fe) 3+ +Na0H→Fe(0H) 3 ↓+Na +
Al 3+ +Na0H→Al(0H) 3 ↓+Na +
So that iron ions generate ferric hydroxide precipitates and aluminum ions generate aluminum hydroxide precipitates; the calcium ion, the manganese ion and the magnesium ion still exist in the solution in the form of ions; the second solid phase contains ferric hydroxide and aluminum hydroxide after detection; the main components in the second solution are magnesium ions, calcium ions, manganese ions and sodium ions;
S6：CO 2 introducing the second solution to react to remove impurities of calcium, and then carrying out suction filtration to obtain a third solution and a third solid phase;
specifically, in a high-pressure reaction kettle, CO 2 Introducing the second solution until no new precipitate is generated; the suction filtration can be carried out through a buchner funnel, a suction filtration bottle, a circulating vacuum pump and the like for solid-liquid separation;
the reaction occurring in step S6 is as follows: CO 2 +H 2 O→H 2 CO 3 ，Ca 2+ +CO 3 2- →CaCO 3 ↓
The third solid phase comprises calcium carbonate as detected; the main component in the third solution is manganese ion and magnesium ion;
s7: adding an alkaline solution to adjust the pH value of the third solution to 9-12, and then carrying out suction filtration to obtain a fourth solution and a fourth solid phase;
specifically, the alkaline solution used in step S7 is sodium hydroxide or potassium hydroxide solution, preferably sodium hydroxide solution, preferably pH 12; at this time, manganese ions are completely precipitated;
the reaction occurring in step S7 is as follows: mn (Mn) 2+ +2OH - →Mn(OH) 2
The fourth solid phase comprises manganese hydroxide after detection; the fourth solution contains magnesium ions as the main component;
s8: adding an alkaline solution to adjust the pH value of the fourth solution to 13-14 to generate magnesium hydroxide precipitate, and then filtering to separate magnesium hydroxide solid;
specifically, the alkaline solution used in step S8 is sodium hydroxide or potassium hydroxide solution, preferably sodium hydroxide solution, preferably pH 14; at this time, magnesium ions are completely precipitated;
the reaction occurring in step S8 is as follows: mg of 2+ +2OH - →Mg(OH) 2 ↓；
S9: washing and drying manganese hydroxide and magnesium hydroxide for multiple times to obtain a high-purity manganese magnesium product;
washing manganese hydroxide and magnesium hydroxide by distilled water, and drying at 80 ℃ for 2 hours by using an electrothermal blowing box.
Testing the obtained magnesium element and manganese element, wherein the test is measured by a scientific compass test platform; the device is as follows: czech TESCAN MIRA LMS; the test conditions were: and (3) metal spraying target material: pt; taking a trace sample/block/film sample, directly adhering the trace sample/block/film sample to conductive adhesive, and spraying metal for 45s by using a Quorum SC7620 sputtering film plating instrument, wherein the metal spraying is 10mA; then using a TESCAN MIRA LMS scanning electron microscope to shoot the shape of a sample, the energy spectrum mapping and other tests, wherein the accelerating voltage is 3kV during shape shooting, 15kV during energy spectrum mapping shooting, and the detector is an SE2 secondary electron detector; SEM-EDS graphs of magnesium element and manganese element are obtained.
As shown in the SEM-EDS diagram of magnesium element of fig. 5, the abscissa of SEM-EDS diagram is energy (energy), in KeV, and the ordinate is signal intensity, in cps/eV; the mass ratio and the atomic ratio of the sample are shown in the following table 1, and the mass ratio and the atomic ratio of the sample accord with the chemical structure of magnesium oxide;
as shown in the SEM-EDS diagram of manganese element of fig. 6, the SEM-EDS diagram has an abscissa of energy (KeV) and an ordinate of signal intensity (cps/eV); the mass ratio and atoms of the sample are detected as shown in figure 7, and conform to the chemical structure of manganese oxide;
the brown yellow substance generated by oxidizing manganese hydroxide with oxygen in air is manganese metahydroxide precipitate MnO (OH) 2 The chemical structure of MnO is therefore present in SEM-EDS.
Examples
S1: mixing the coarse gas slag and the fine gas slag in a ratio of 5:1 to form gas slag, crushing and grinding, wherein the grinding particle size is 300 meshes.
S2: crushing and grinding the gasified slag after S1; adding sodium carbonate according to the proportion of 20:1, stirring uniformly, and heating and activating in a trolley furnace; the roasting temperature is 730 ℃, the heating rate is 15 ℃/min, and the roasting time is 40min.
S3: dissolving gasified slag tailings after the activation in the step S2 in water, and continuously stirring and dispersing; stopping stirring until no precipitate is dissolved, and obtaining a solid-liquid mixture.
S4: adding 31% hydrochloric acid into the solid-liquid mixture obtained in the step S3 for dissolution, and stirring at 80 ℃ in a hot water bath; until the precipitate is no longer dissolved; and then carrying out suction filtration to obtain a first solution and a first solid phase.
S5: and adding sodium hydroxide solution to adjust the pH value of the first solution to 8, and then carrying out suction filtration to obtain a second solution and a second solid phase.
S6：CO 2 Introducing the second solution until no new precipitate is generated; and then carrying out suction filtration to obtain a third solution and a third solid phase.
S7: and adding sodium hydroxide solution to adjust the pH value of the third solution to 12, and then carrying out suction filtration to obtain a fourth solution and manganese hydroxide.
S8: and adding sodium hydroxide solution to adjust the pH value of the fourth solution to 14, generating magnesium hydroxide sediment, and then filtering to separate magnesium hydroxide solid.
S9: the magnesium hydroxide and the manganese hydroxide are washed by distilled water, and then dried by an electric heating air blowing box, wherein the drying temperature is 85 ℃ and the drying time is 2 hours.
The influence on the activated gasification slag by adding the coarse slag of the gas gasification slag alone and adding the fine slag of the gas gasification slag alone under the mixing of the coarse slag and the fine slag is studied below.
Comparative example 1
In this comparative example, the same amount of crude gas-converted slag as in example was added alone, and the other conditions were the same as in example.
Comparative example 2
In this comparative example, the same amount of the fine slag of the gas slag as in example was added alone, and the crushing and grinding were not performed, and the other conditions were the same as in example.
Experimental results
As shown in Table 2 below, examples of the present application and comparative examples 1 and 2 are shown, activated gasified slag was obtained and analyzed
From the above table analysis, it follows that: after the coarse slag and the fine slag of the gas slag are mixed, the carbon content in the fine slag is about 30-50%, the carbon can be burnt during roasting, the heat of the fine slag directly acts on the surface and the inner reaction area of the gas slag, and the reaction efficiency is increased.
The embodiments of the present invention described above do not limit the scope of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention as set forth in the appended claims.
Claims (10)
1. A method for separating manganese and magnesium components in coal gas slag is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing coarse slag and fine slag of the gas-converted slag, and crushing and grinding;
s2: uniformly mixing the crushed coal gas slag of the S1 with active metal carbonate, and heating and activating by using medium-low temperature continuous heating equipment;
s3: dissolving the gasified slag in water after activation, and continuously stirring and dispersing to form a solid-liquid mixture;
s4: adding hydrochloric acid into the solid-liquid mixture obtained in the step S3 for dissolution, and stirring in a hot water bath; suction filtration is carried out to obtain a first solution and a first solid phase;
s5: adding an alkaline solution, regulating the pH value of the first solution to 7-9, and then carrying out suction filtration to obtain a second solution and a second solid phase;
s6: introducing CO into the second solution 2 Then suction filtration is carried out to obtain a third solution and a third solid phase;
s7: adding an alkaline solution, regulating the pH value of the third solution to 9-12, and then carrying out suction filtration to obtain a fourth solution and a fourth solid phase; the fourth solid phase contains manganese hydroxide, and the main component in the fourth solution is magnesium ions;
s8: adding an alkaline solution to adjust the pH value of the fourth solution to 13-14, and generating magnesium hydroxide sediment;
s9: washing and drying manganese hydroxide and magnesium hydroxide.
2. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in the step S1, the mixing ratio of the coarse coal gasification slag to the fine coal gasification slag is 5:1-1.5.
3. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: the carbonate of the active metal in step S2 may be any of sodium carbonate and potassium carbonate.
4. A method for separating manganese and magnesium components from gas slag according to claim 3, wherein: in the step S2, the mixing ratio of the gasified slag and the sodium carbonate is 15-30:1.
5. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in the step S2, the roasting temperature of the medium-low temperature continuous heating equipment is 550-750 ℃, the heating rate is 10-20 ℃/min, and the roasting time is 20-60min.
6. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in the step S4, the mass fraction of hydrochloric acid is 31%, and the mixture is stirred for 10 minutes, and the temperature of the hot water bath is 80 ℃.
7. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: the alkaline solution used in the steps S5, S7 and S8 is sodium hydroxide or potassium hydroxide solution.
8. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in step S5, the pH value of the first solution is adjusted to 8.
9. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in step S7, the pH of the second solution is adjusted to 12.
10. The method for separating manganese and magnesium components from the gas slag according to claim 1, which is characterized by comprising the following steps: in step S8, the pH of the third solution is adjusted to 14.
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